Detergent and tableware cleaner

ABSTRACT

A mixture comprising 
     (a) from 0.1 to 99% by weight of at least one polycarboxylate having at least 3 carboxyls, 
     (b) from 0.1 to 99% by weight of at least one amine having a pK a  value of more than 9, and 
     (c) from 0.1 to 99% by weight of at least one acid selected from the group consisting of mineral acids and organic acids having one or two carboxyls and not more than 10 carbons, 
     with the proviso that the mixture contains less than 24% by weight of triphosphates, is used in detergent and rinse aid formulations.

The invention relates to mixtures comprising at least onepolycarboxylate, at least one amine and at least one acid, to detergentscontaining them, and to their use as encrustation inhibitors indetergents and as encrustation inhibitors and scale inhibitors in rinseaids.

BE 773 260 describes detergents containing in addition to LAS andtripolyphosphate as softener component N-alkylpropanediamines,especially N-dodecylpropane-1,3-diamine, N-cocopropane-1,3-diamine orN-tallow fatty-propane-1,3-diamine.

EP-A-0 173 398 describes detergent compositions comprising a mixture oflong-chain primary or secondary amines and cellulase as the essentialtextile softener ingredients. The amine used can be tallow fatty amine.The compositions may include alkali metal phosphates andpolycarboxylates in addition to LAS and sodium triphosphate.

WO 86/07603 describes detergents for low washing temperatures which maycontain ether amines, amido amines, glucamine or morpholine derivatives,and polycarboxylic acids.

GB-A-2 172 910 describes detergent compositions having textile softenerproperties. For this purpose use is made of specific primary, secondaryor tertiary amines having a long-chain hydrocarbyl radical, especiallyN,N-dimethyllaurylamine or N-dimethylcocoamine, which may be mixed witha Broöstedt acid as dispersant. Acids mentioned include inorganic acidsand organic acids, such as polymeric carboxylic acids. Monocarboxylicacids are preferred. The composition include LAS and sodiumtripolyphosphate.

DE-A-195 32 717 describes detergents containing modified polyasparticacids as encrustation inhibitors. The polyaspartic acids arepolycondensation products of aspartic acid, certain amines, andphosphorus-containing acids.

WO 95/33035 describes detergent compositions which are particularlyeffective for removing fatty or oily dirt from substrates such astextile products or crockery. One detergent composition contains 0.5% byweight of 1-hexylamine, 9.0% by weight of C₁₂₋₁₆ fatty acid and 6.0% byweight of anhydrous citric acid, and also 10.0% by weight of oleylsarcosinate.

It is an object of the present invention to provide encrustationinhibitors for detergents and rinse aids.

It is another object of the present invention to provide encrustationinhibitors for reduced-phosphate or phosphite-free detergents and rinseaids.

It is yet another object of the present invention to provide detergentsand rinse aids comprising novel encrustation inhibitors.

It is a further object of the present invention to provide encrustationinhibitors for detergents and rinse aids which are easier to preparethan the aspartic acid polycondensates and which have a better action.

It is a further object to provide scale inhibitors for dishwashingcompositions.

It is a further object to provide dishwashing compositions whichcomprise scale inhibitors.

It is a further object to provide scale inhibitors for dishwashingcompositions that have a better action than conventionalpolycarboxylates.

We have found that these objects are achieved by a mixture comprising

(a) from 0.1 to 99% by weight of at least one polycarboxylate having atleast 3 carboxyls,

(b) from 0.1 to 99% by weight of at least one amine having a pK_(a)value of more than 9, and

(c) from 0.1 to 99% by weight of at least one acid selected from thegroup consisting of mineral acids and organic acids having one or twocarboxyls and not more than 10 carbons,

with the proviso that the mixture contains less than 24% by weight oftriphosphates and the total amount of the ingredients is 100% by weight,and by the use of this mixture in detergent or rinse aid formulations.

It has been found in accordance with the invention that mixturescomprising

(a) from 0.1 to 99% by weight, preferably from 30 to 97% by weight, inparticular from 50 to 95% by weight, of at least one polycarboxylatehaving at least 3 carboxyls,

(b) from 0.1 to 99% by weight, preferably from 0.5 to 50% by weight, inparticular from 1 to 25% by weight, of at least one amine having apK_(a) of more than 9, preferably from 9.5 to 12, and

(c) from 0.1 to 99% by weight, preferably from 0.3 to 50% by weight, inparticular from 0.5 to 40% by weight, of at least one acid selected fromthe group consisting of mineral acids and organic acids having one ortwo carboxyls and not more than 10 carbons,

with the proviso that the mixture contains less than 24% by weight,preferably not more than 20% by weight, of triphosphates and the totalamount of the ingredients is 100% by weight, haveencrustation-inhibiting and scale-inhibiting properties which are betterthan those of pure polycarboxylates as described, for example, inDE-A-195 32 717.

A description will first be given of components (a), (b) and (c) of thenovel mixtures.

Component (a)

Polycarboxylates which can be used in accordance with the invention haveat least three carboxyl groups. These novel polycarboxylates may bemonomeric compounds or may be polymeric compounds having a molecularweight distribution. It is possible to employ both naturally occurringand synthetic polycarboxylates. According to a preferred embodiment, thepolycarboxylates used are biodegradable or can be eliminated in sewageplants. According to one embodiment of the invention, the weight-averagemolecular weights of the polycarboxylates are from 100 to 300,000,preferably from 800 to 500,000, in particular from 800 to 200,000.

According to one embodiment of the invention, low molecular masscarboxylates having 3 to 10 carboxyls are used. Examples of suitable lowmolecular mass polycarboxylates are those of citric acid, isocitricacid, nitrilotriacetic acid, ethylenediaminetetraacetic acid,isoserinediacetic acid, β-alaninediacetic acid,diethylenetriaminepentaacetic acid, hydroxyethyldiamine triacetic acid,propylenediaminetetraacetic acid, methylglycinediacetic acid,cyclohexanehexacarboxylic acid and alkylglycinediacetic acids having 2to 24 carbons in the alkyl radical. According to one embodiment of theinvention, the carboxylates are devoid of aromatic radicals.

Examples of polycarboxylates which can be used according to oneembodiment of the invention are proteins containing aspartic acid orglutamic acid, such as casein, gelatine, wheat proteins, soya proteins,pea proteins, polyaspartic acid, polyglutamic acid, andpolycocondensates of aspartic acid and/or carboxylic acids. According toone embodiment of the invention it is advantageous to lower themolecular weight of the proteins, preferably to a weight-averagemolecular weight of from 800 to 200,000, by subjecting them, forexample, to an oxidative, reductive or hydrolytic treatment. Hydrolytictreatment can be carried out with the aid of enzymes, acids or bases.

Other polycarboxylates which can be used are polymeric sugar acids, suchas pectic acid, or oxidized polysaccharides, such as oxidized starch,oxidized maltodextrins or oxidized cellulose. The degree of oxidationmay differ. For example, in the case of starch only the primary CH₂OHgroups in position C₆ to the carboxyl group may be oxidized, with theformation of monocarboxy starch. However, oxidation may also occur withdiol cleavage between C₂ and C₃ to form the dialdehyde starch, andfurther oxidation to the dicarboxy starch , or with oxidation of allthree carbons in positions C₆, C₂ and C₃, to give the tricarboxy starch.All oxidized polysaccharides of this type can be employed, preferablythose having a weight-average molecular weight of from 800 to 500,000.The polysaccharides may also be etherified or esterified. Etherificationcan be carried out with the chloroacetic acid. Examples arecarboxylmethyl starch or carboxylmethylcellulose. Examples of esterifiedstarches are acid citric esters of the starches, which are prepared byesterifying starch with excess citric acid.

According to one embodiment of the invention it is also possible toemploy polyesters which have been prepared by esterifying polyols, suchas ethylene glycol, polyethylene glycol, polyalkylene glycols, glycerol,mannitol, sorbitol and polyvinyl alcohol, with citric acid, tartaricacid or malic acid, or butanetetracarboxylic acid.

Synthetic polycarboxylates which can be used in accordance with oneembodiment of the invention are advantageously prepared by free-radicalpolymerization of unsaturated monomers. Examples of monomers employedare acrylic acid, maleic acid, maleic anhydride, methacrylic, itaconic,aconitric, vinylsulfonic, methallylsulfonic and cinnamic acid, acrylicesters, such as methyl, butyl, ethylhexyl, oleyl and stearyl acrylatesand tallow fatty alcohol acrylate, mono- and dialkyl maleates, such asmono- and dimethyl maleates, mono- and diethyl maleates, mono- anddiisopropyl maleates, mono- and dibutyl maleates, and mono- anddistearyl maleates. In addition to the unsaturated carboxylic acids itis also possible for up to 90% of other monomers, such as vinyl acetate,vinyl propionate, vinylsulfonic acid, vinyl stearate, styrene, olefinssuch as ethylene, propylene, butene, isobutene, diisobutene, hexene,octene, octadecene, C₂₀/C₂₄ olefin, cyclopentene, cyclopentadiene,cyclohexene, and butadiene, and vinyl ethers such as methyl vinyl ether,isobutyl ethers, butanediol monovinyl ether ethoxylates, allyl alcoholethyoxylates or furan to be present. The polycarboxylates are preparedby known methods of free-radical polymerization in the form of asolution or precipitation polymerization in water, polyalkylene glycols,nonionic surfactants, acetone, toluene, o-xylene, isopropanol or otherorganic solvents. Free-radical initiators used are all initiators whichare customarily employed. If low molecular mass polymers are desired itis also possible to carry out polymerization in the presence ofregulators. According to one embodiment of the invention, thepolycarboxylates are used in the form of the sodium or potassium salt.This applies in particular to copolymers of maleic anhydride, which areusually insoluble in water and other solvents. In the hydrolyzed alkalimetal salt form, then, they are usually soluble or at least dispersiblein water.

Also suitable according to one embodiment of the invention are graftpolymers of acrylic acid, methacrylic acid, maleic acid, vinylsulfonicacid, methallylsulfonic acid, methacrylic acid and glucose,polysaccharides, such as starch or starch hydrolyzates, proteins,protein hydrolyzates or polyalkylene glycols. Examples are graftpolymers of acrylic acid and maleic acid on maltodextrins, graftpolymers of maleic acid and starch, graft polymers of acrylic acid andcasein, and graft polymers of acrylic acid, methyl methacrylate andgelatin.

Typical polycarboxylates which can be employed according to theinvention are polyacrylic acids having molecular weights of between1,000 and 250,000, 70/30 acrylic acid-maleic acid copolymers with amolecular weight of 70,000, 40/60 acrylic acid-maleic acid copolymerswith a molecular weight of 40,000, maleic acid-isobutene copolymers witha molecular weight of 4,000, maleic acid-diisobutene copolymers with amolecular weight of 12,000, maleic acid-styrene copolymers with amolecular weight of 20,000, maleic acid-C₂₀/C₂₄ olefin copolymers with amolecular weight of 15,000, polyvinylsulfonic acid with a molecularweight of 1,000, polymaleic acid with a molecular weight of 1,000,polyaspartic acids with molecular weights of between 1,000 and 50,000,acrylic acid-maleic acid-vinyl acetate terpolymers with a molecularweight of 40,000, graft polymers of acrylic acid and maleic acid onmaltodextrins, with a molecular weight of 40,000, graft polymers ofacrylic acid and polyethylene glycols, with a molecular weight of60,000, and graft polymers of acrylic and maleic acids and polyethyleneglycols, with a molecular weight of 20,000.

According to one embodiment, the polycarboxylates are devoid of aromaticradicals.

Components (b)

As component (b) of the novel mixtures use is made of at least one aminehaving a pK_(a) of more than 9, preferably from 9.5 to 12.

According to one embodiment the amines contain only aliphatic,cycloaliphatic and/or araliphatic radicals, the latter being those inwhich aromatic radicals are attached via alkylene to the amine nitrogen.

According to one embodiment of the invention, the amines which can beused have the formula (II)

R⁵NR⁹—[(CR⁷R⁸)_(m)—NH]_(n)—R⁶   (II)

where n is an integer from 0 to 20 and m is an integer from 1 to 4, R⁵is a C₁₋₃₀, preferably C₁₋₂₀, in particular C₁₋₁₀ alkyl, or C₂₋₃₀,preferably C₂₋₂₀, in particular C₂₋₁₀ alkenyl and each of R⁶, R⁷, R⁸ andR⁹ independently is hydrogen or is as defined for R⁵.

According to one embodiment of the invention n is zero, R⁵ is C₆₋₂₀alkyl or an alkenyl, R⁶ is C₁₋₄ alkyl or C₂₋₄ alkenyl, and R⁹ ishydrogen, C₁₋₄ alkyl or C₂₋₄ alkenyl.

According to one embodiment of the invention, when used in a detergentthe amine has a pK_(a) which is greater than the pH minus 1, preferablygreater than the pH, particularly preferably at least 0.5 greater thanthe pH of the 1% strength liquor formed from the detergent. In thiscontext the pK_(a) is the value for the corresponding acid of theamine—that is to say, of the protonated amine—and is equal to 14-pK_(b)of the amine.

As component (b) it is preferred to employ mono- or polyamines,preferably having at least 4 carbons. The amines may be primary,secondary or tertiary and may be hydrophilic or hydrophobic.

According to one embodiment of the invention, component (b) comprisesprimary amines having preferably 3 to 20, especially 4 to 10, carbons,such as butylamine, tert-butylamine, sec-butylamine, ethylhexylamine,2-methylheptylamine, octylamine, 2-ethylhexylamine, nonylamine,decylamine, 2-propylheptylamine, undecylamine, cetylamine,tridecylamine, isotridecylamine, fatty amines, such as oleylamine,stearylamine, octadecylamine, tallow fatty amine, hydrogenated tallowfatty amine, amines based on coconut fatty acids, polyisobutenamine,polypropylenamine, alkyl polyethylene oxide amines which can be preparedby aminating alkyl polyglycols. Polyfunctional primary amines are, forexample, 1,6-diaminohexane, 1,8-diaminooctane, 1,3-diaminopropane,isophoronediamine, polyoxyalkylenediamines, such as polyethylene oxidediamine, polypropylene oxide diamine, polybutylene oxide diamine,polytetrahydrofurandiamine, co(polyethylene oxide/propylene oxide)amineswhich can be prepared by aminating polyalkylene oxides, and aminatedalkoxylated fatty alcohols and oxo alcohols, such as aminated reactionproducts of one mole of C₁₆/C₁₈ oxo alcohol and seven moles of ethyleneoxide, which has been subsequently aminated. These types of amine can betermed ether amines.

According to one embodiment of the invention, component (b) comprisessecondary dialkyl amines having preferably 5 to 40, especially 8 to 46carbons, such as N,N-dibutylamine, N,N-dihexylamine,N,N-diisopentylamine, N,N-dipentylamine, N,N-diethylhexylamine,N,N-di-tallow fatty amine, hydrogenated N,N-di-tallow fatty amine,N,N-distearylamine, N,N-dioleylamine, mixed secondary amines such asN-methyl-N-octylamine, N-methyl-N-stearylamine, N-methyl-N-tallow fattyamine, hydrogenated N-methyl-N-tallow fatty amine,N-methyl-N-decylamine, N-methyl-N-octyl amine,N-methyl-N-ethylhexylamine, alkanolamines, or reaction products ofprimary and secondary amines with 1-100 mol, preferably 1-20 mol,especially 1-15 mol of ethylene oxide and/or propylene oxide, such asreaction products of isotridecylamine with 7 mol of ethylene oxide,reaction products of N-methyl-N-tallow fatty amine with 10 mol ofethylene oxide and 3 mol of propylene oxide, of tallow fatty amine with1 mol of ethylene oxide, oleylamine with 3 mol of ethylene oxide, oftallow fatty amine with 3 mol of ethylene oxide and 1 mol of propyleneoxide, of hydrogenated tallow fatty amine with 2 mol of ethylene oxide,and of stearylamine with 1 mol of ethylene oxide. According to oneembodiment of the invention it is also possible to use reaction productsof primary and secondary amines with other epoxides, such as mono- andpolyfunctional glycidyl ethers, such as butyl glycidyl ether, ethylhexylglycidyl ether, C₁₂/C₁₄ alcohol glycidyl ether, C₁₃/C₁₅ alcohol glycidylether, 1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether,phenyl glycidyl ether, o-cresyl glycidyl ether, and polypropyleneglycidyl ethers. As epoxides it is possible in accordance with theinvention also to use long-chain epoxides, for example epoxidized castoroil, or alkyloxiranes which can be prepared by epoxidation of olefins,such as propyloxirane, decyloxirane, dodecyloxirane andoctadecyloxirane.

According to one embodiment of the invention it is also possible toemploy tertiary amines, preferably those having 6-60, especially 9-54,carbons. Examples are tributylamine, trioctylamine, tridecylamine,tridodecylamine, dimethyldodecylamine, dimethyllaurylamine, dimethylcoconut fatty amine, dimethylcetylamine, dimethylstearylamine,dimethyloctadecylamine, methyl-dioctylamine, methyldodecylamine,methyldi-coconut oil amine, methyldi-tallow fatty amine, hydrogenatedmethyldi-tallow fatty amine, methyldioctadecylamine,dimethyl-C₁₂/C₁₄-amine, N,N-dimethylcyclohexylamine.

According to one embodiment of the invention it is also possible toemploy polyfunctional amines which possess not only primary amino butalso secondary or tertiary amino groups, preferably with 3 to 60,especially 4 to 40 carbons, examples being alkylaminoalkylamines such as2-ethylaminoethylamine, tallow fatty aminopropylamine, hydrogenatedtallow fatty aminopropylamine, coconut oil-aminopropylamine,oleylaminopropylamine (commercially available, for example, as Duomeen®from Akzo), 3-isopropylaminopropylamine, or dialkylaminoalkylamines,such as 3-methyl-tallow fatty aminopropylamine, 3-di-tallow fattyaminopropylamine, 2-dimethylaminoethylamine,1-diethylamino-4-aminopentane and dimethylaminopropylamine.

According to one embodiment of the invention it is also possible toemploy oligomeric or polymeric amines having, for example, secondaryamino groups, preferably with a weight-average molecular weight of from100 to 250,000, in particular from 200 to 100,000. Examples arediethylenetriamine, triethylene tetraamine, polyethyleneimine,polyvinylamine, copolymers of vinylamine and vinylformamide,alkylaminopolyalkyleneamines, such as N-tallow fattytripropylenetetraamine, or dialkylamino-polyalkyleneamines, such asN,N-di-tallow fatty dipropylene triamine.

Futhermore, according to one embodiment of the invention it is possibleto employ amido amines, preferably those having a weight-averagemolecular weight of from 200 to 100,000, in particular from 250 to80,000, which can be prepared by subjecting mono- and polybasiccarboxylic acids and at least difunctional amines to condensation andwhich contain at least one basic amino group, examples being acondensation product of 1 mol of stearic acid with 1 mol ofhexamethylenediamine, a condensation product of 1 mol of oleic acid with1 mol of ethylenediamine, a condensation product of 1 mol of C₁₀/C₁₂fatty acid with 1 mol of isophoronediamine, a condensation product of 1mol of adipic acid with 2 mol of hexamethylenediamine, a condensationproduct of 1 mol of phthalic acid with 2 mol of ethylenediamine, acondensation product of 1 mol of oleic acid with 1 mol ofethylenediamine, a condensation product of 2 mol of adipic acid with 3mol of hexamethylenediamine, a condensation product of 3 mol ofterephthalic acid with 2 mol of butylenediamine, and a condensationproduct of 4 mol of adipic acid with 3 mol of hexamethylenediamine.

As amines it is possible, in accordance with one embodiment of theinvention, to employ ester amines as well, preferably those having aweight-average molecular weight of from 200 to 100,000, in particularfrom 300 to 10,000, which can be prepared by esterification ofalkanolamines with carboxylic acids, examples being esters of stearicacid and ethanolamine, esters of oleic acid andN,N-dimethylethanolamine, esters of tallow fatty acid anddiethanolamine, esters of coconut fatty acid and triethanolamine, andesters of phthalic acid and ethanolamine.

It is also possible in accordance with one embodiment of the inventionto employ N-alkyl-, N-alkenyl- or N-hydroxyalkylglucamines, or thecorresponding morpholines, having up to 30 carbons.

The amine preferably comprises at least one amine having at least fourcarbons, preferably tallow fatty amine, hydrogenated tallow fatty amine,octylamine, 2-ethylhexylamine, nonylamine, decylamine,2-propylheptylamine, undecylamine, dodecylamine, tridecylamine,cetylamine, stearylamine, palmitylamine, oleylamine, coconut fattyamine, mono-α-branched secondary amines, bis-α-branched secondary aminesof the formula (I)

R⁴R³HC—HN—CHR¹R²   (I)

where R¹-R⁴ independently of one another are substituted orunsubstituted ₁₋₂₀ alkyls.

Component (c)

Component (c) of the novel mixture is at least one acid selected fromthe group consisting of mineral acids and organic acids having one ortwo carboxyls and containing, according to one embodiment, no aromaticradicals.

Preference is given here to phosphorus-containing acids.

As component (c) it is possible to employ saturated or unsaturatedorganic acids having one or two carboxyls and preferably up to 15carbons, especially up to 10 carbons, such as formic, acetic, propionic,capric, oxalic, succinic, adipic, maleic, fumaric, sebacic, malic,lactic, glycolic, tartaric and glyoxylic acids, and also mineral acids.

Examples of novel mineral acids are hydrochloric, sulfuric, sulfurous,metalsilicic and boric acid, heteropoly acids of tungsten or molybdenum,acidic ion exchangers, acidic silicates or alumosilicates,benzenesulfonic acid, toluenesulfonic acid and naphthalenesulfonic acid.Phosphorus-containing acids are preferably employed, examples beingphosphoric acid, diphosphoric acid, triphosphoric acid, polyphosphoricacid, phosphorous, hypophosphorous acid, phosphonic acid, primary andsecondary phosphoric esters, primary and secondary phosphoramides, suchas 2-ethylhexylphosphoramide, oleylphosphoramide or di-tallow fattyphosphoramide, and also phosphonic acids such as diethylenetriaminepentamethylene phosphnonic acid.

The novel mixtures comprising components (a), (b) and (c) contain, inaccordance with the invention, less than 24% by weight, preferably notmore than 20% by weight, of triphosphate, preferably not more than 10%by weight, and in particular not more than 5% by weight of triphosphate.According to one embodiment of the invention the mixtures aresubstantially or completely free from triphosphate.

The novel mixtures comprising components (a), (b) and (c) containaccording to one embodiment of the invention not more than 20% by weightof LAS, preferably not more than 10% by weight, in particular not morethan 5% by weight of LAS. According to one embodiment of the inventionthe mixtures are substantially or completely free form LAS.

Preparation of the mixtures

To prepare the mixtures, components (a), (b) and (c) can be mixed in anyorder. Preparation of the mixtures (abc) from polycarboxylate (a), amine(b) and acid (c) can be carried out in accordance with the followinggeneral scheme:

b+c→bc (salt formation)

bc→d (conditioning of the salt)

a+bc→abc (blending of polycarboxylate with salt)

a+d→ad

a+b→ab

ab+c→abc

a+c→ac

ac+b→abc

According to one embodiment of the invention the mixtures can beprepared by first of all neutralizing amine (b) and acid (c) at 10°-150°C. and then mixing the neutralization product (e.g. alkylammoniumphosphate) into the polycarboxylate. The neutralization of amines andacids may take place in bulk or in a diluent. If in bulk, the procedureis carried out, for example, in an extruder at from 20° to 150° C., forexample by metering, in accordance with one embodiment of the invention,phosphoric acid and melted tallow fatty amine into the extruder. Thealkylammonium phosphate is discharged as a melt and can be processed inthe form of extrudates or granules. As diluents for the neutralization,in accordance with one embodiment of the invention, it is possible touse water, acetone, methanol, ethanol, glycerol, surfactants, includingnonionic surfactants, such as alkoxylation products of oxoalcohols orfatty alcohols, ethylene glycol, diethylene glycol, triethylene glycol,polyalkylene glycols, propylene glycol, dipropylene glycol,polypropylene glycol, copolymers of ethylene oxide and propylene oxide,and block-linked polyethylene glycols and polypropylene glycols.

If phosphoric acid is used as component (c), the mixtures canadvantageously be prepared, in accordance with one embodiment of theinvention, by first of all neutralizing alkylamines and phosphoric acidsat from 10° to 150° C. and then heating the salt-like neutralizationproducts at up to 250° C. At from 150° to 250° C. the conditionedalkylammonium phosphates undergo at least partial conversion, withelimination of water, into alkylammonium polyphosphates andalkylaminephosphoramides (component (d)). Condensation can be carriedout in a diluent or, preferably, in bulk. Suitable diluents arehigh-boiling diluents such as glycerol, surfactants, including nonionicsurfactants, ethylene glycol, diethylene glycol, triethylene glycol,polyalkylene glycols, propylene glycol, dipropylene glycol,polypropylene glycol, copolymers of ethylene glycol and propyleneglycol, and block-linked polyethylene glycols and polypropylene glycols.The reaction apparatus used may be an extruder, compounder or paddledrier. The conditioned adducts of alkylamine with phosphoric acids arethen mixed in with the polycarboxylate.

According to one embodiment of the invention the isolation of thereaction product of amine with acid can be avoided by using thepolycarboxylate (a) in the form of an aqueous solution or, if it is notentirely soluble in water, then in the form of a suspension and addingfirst acids (c) and then amines (b). In the case of this procedure thepolycarboxylates can be employed in the form of the anhydrides, acidforms or alkali metal salt forms. If the anhydrides or acids are used,then neutralization with alkalis can be carried out after adding theamines (b) and acids (c).

According to one exemplary embodiment of the invention, the mixtures canbe prepared by adding first amines (b) and then acids (c) to thepolycarboxylates (a) in the form of an aqueous solution or suspension.Subsequent neutralization can be carried out as described above.

If polymerization produces anhydrides of the polycarboxylates, then inaccordance with one embodiment of the invention these anhydrides, too,can be blended with components (b) and (c). This can then be followed byhydrolysis with alkalis and conversion to an aqueous solution orsuspension.

In detergents, the polycarboxylates are customarily employed in the formof the alkali metal salts. The polycarboxylates can be neutralizedbefore or after the alkylamine and phosphoric acid have been mixed in.In most cases the mixtures are then neutralized to a pH of 6-10.

If the polycarboxylates are obtainable in solid form, then thepolycarboxylate powders or granules can also be blended with the saltsof (b) and (c). Solid polycarboxylates may be obtained in the form ofpowders or granules. For example, a solution of a copolymer of acrylicand maleic acid or its salt can be converted into a solid powder byspray drying or spray granulation. In the case of the precipitationpolymerization of maleic anhydride and isobutene in organic solvents, asolid polycarboxylate powder is produced which contains thepolycarboxylate in the anhydride form. Such or similarly prepared solidpolycarboxylates can then be blended with solid adducts of the amines(b) and acids (c). The solid adducts of (b) and (c) are obtained, forexample, by reacting tallow fatty amine and phosphoric acid in theextruder and then shaping the melt, or by neutralizing the amines (b)and the acids (c) in a diluent in which the adduct of (b) and (c) isinsoluble and precipitates. For example, 2-ethylhexylamine or tallowfatty amine can be reacted with phosphoric acid or polyphosphoric acidin acetone or toluene, so that the adduct is produced in the form of apowder.

The procedural options are illustrated below by way of example:

According to one embodiment of the invention, maleic anhydride andisobutene are subjected to free-radical precipitation polymerization inan organic solvent and the resulting polymer, in the anhydride form, isisolated by filtration. This anhydride-form polymer is suspended inwater, alkylammonium phosphate is added, and then the mixture isneutralized with sodium hydroxide solution.

According to one embodiment of the invention it is also possible tohydrolyze the polymer of maleic anhydride and isobutene with sodiumhydroxide solution, to give an aqueous sodium salt solution, and then toadd alkylammonium phosphate. The aqueous sodium salt solution of themaleic acid-isobutene copolymer can also have added to it firstalkylamine and then phosphoric acid. However, it is also possible to addfirst phosphoric acid and then tallow fatty amine. Another possibilityis first to prepare a condensation product of tallow fatty amine andphosphoric acid, at 200° C., and then to add this to the aqueous sodiumsalt solution of the copolymer.

According to one embodiment of the invention it is possible to take anaqueous solution of polyacrylic acid in the acid form and to add firstalkylamine and then phosphoric acid to it.

According to one embodiment of the invention it is possible first of allto neutralize a solution of polyacrylic acids with sodium hydroxidesolution and then to add tallow fatty alkylphosphoramide.

The novel mixtures (abc) may give clear solutions in water. However,they may also form suspensions if one or more components of the mixture(abc) is insoluble in water. In such cases it may be useful to produce avery finely divided suspension by means of intensive stirring orshearing. This can be achieved with the aid of a dispersing andhomogenizing machine, an intensive mixer, a high-speed rotating stirrerelement equipped with cutting blades, a calender, or with the action ofultrasound.

The novel mixtures can be used in detergents, especially as encrustationinhibitors or scale inhibitors. In addition, they can be used in rinseaid formulations, especially as encrustation inhibitors or scaleinhibitors.

Detergent formulations

The invention also relates to detergent formulations comprising at leastone surfactant and a mixture of

(a) at least one polycarboxylate having at least three carboxyl groups,

(b) at least one amine whose pK_(a) value is greater than the pH,reduced by 1, of a 1% strength liquor of the detergent,

(c) at least one acid selected from the group consisting of mineralacids and organic acids having one or two carboxyls and not more than 10carbons,

and, if desired, other customary constituents, with the proviso that thedetergent contains less than 24% by weight of triphosphate.

The invention additionally relates to detergents comprising at least onesurfactant and a novel mixture with, if desired, other customaryconstituents.

According to one embodiment the detergents contain from 0.01 to 40% byweight, preferably from 0.1 to 30% by weight, in particular from 0.5 to20% by weight of component (a), from 0.01 to 20% by weight, preferablyfrom 0.03 to 10% by weight, in particular from 0.05 to 5% by weight, ofcomponent (b), and from 0.01 to 20% by weight, preferably from 0.02 to10% by weight, in particular from 0.03 to 8% by weight, of component(c).

The mixtures of (a), (b) and (c) are employed in accordance with oneembodiment in a proportion of form 0.1 to 20% by weight, preferably from1 to 15% by weight, in detergent formulations.

The detergents can be in powder form or else in a liquid formulation.The composition of the detergents and cleaners may vary widely.Detergents and cleaner formulations normally contain from 2 to 50% byweight of surfactants and, where appropriate, builders. These data applyboth to liquid and to powder detergents. Detergent and cleanerformulations customary in Europe, the USA and Japan are tabulated, forexample, in Chemical and Engn. News, 67 (1989) 35. Further details onthe composition of detergents and cleaners are to be found in UllmannsEnzyklop{umlaut over (a)}die der technischen Chemie, Verlag Chemie,Weinheim 1983, 4th Edition, pp. 63-160.

Reduced-phosphate detergents means formulations which contain not morethan 25% by weight of phosphate, calculated as pentasodium triphosphate.The detergents can be heavy duty detergents or specialty detergents.Suitable surfactants are both anionic and nonionic, or mixtures ofanionic and nonionic, surfactants. The preferred surfactant content ofthe detergents is from 8 to 30% by weight.

Surfactants

Examples of suitable anionic surfactants are fatty alcohol sulfates offatty alcohols with 8 to 22, preferably 10 to 18, carbons, such asC₉-C₁₁-alcohol sulfates, C₁₂-C₁₃-alcohol sulfates, cetyl sulfate,myristyl sulfate, palmityl ulfate, stearyl sulfate and tallow fattyalcohol sulfate.

Other suitable anionic surfactants are sulfated, ethoxylatedC₈-C₂₂-alcohols or their soluble salts. Compounds of this type areprepared, for example, by initially alkoxylating a C₈-C₂₂-alcohol,preferably a C₁₀-C₁₈-alcohol, and then sulfating the alkoxylationproduct. Ethylene oxide is preferably used for the alkoxylation, inwhich case from 2 to 50 mol, preferably from 3 to 20 mol, of ethyleneoxide are employed per mole of fatty alcohol. However, the alcohols canalso be alkoxylated using propylene oxide alone and, where appropriate,butylene oxide. Also suitable are those alkoxylated C₈-C₂₂-alcoholswhich contain ethylene oxide and propylene oxide or ethylene oxide andbutylene oxide. The alkoxylated C₈-C₂₂-alcohols may contain the ethyleneoxide, propylene oxide and butylene oxide units in the form of blocks orin random distribution.

Further suitable anionic surfactants are alkylsulfonates, such asC₈-C₂₄-, preferably C₁₀-C₁₈-alkanesulfonates, and also soaps, such asthe salts of C₈-C₂₋-carboxylic acids.

Other suitable anionic surfactants are N-acylsarcosinates havingaliphatic saturated or unsaturated C₈-C₂₅-acyl radicals, preferablyC₁₀-C₂₀-acyl radicals, such as N-oleylsarcosinate.

Further suitable anionic surfactants are any C₉-C₂₀-linearalkylbenzenesulfonates (LAS). The novel polymers are preferably employedin low-LAS detergent formulations containing less than 4% of LAS,particularly preferably in LAS-free formulations.

The anionic surfactants are preferably added to the detergent in theform of salts. Suitable cations in these salts are ions of alkali metalssuch as sodium, potassium and lithium, and ammonium ions, such as inhydroxyethylammonium, di(hydroxyethyl)ammonium andtri(hydroxyethyl)ammonium salts.

Examples of suitable nonionic surfactants are alkoxylatedC₈-C₂₂-alcohols. Alkoxylation can be carried out with ethylene oxide,propylene oxide and/or butylene oxide. As surfactant in this connectionit is possible to employ all alkoxylated alcohols which contain at leasttwo molecules of one of the abovementioned alkylene oxides in theadduct. Also suitable in this connection are block polymers of ethyleneoxide, propylene oxide and/or butylene oxide, or adducts which containsaid alkylene oxides in random distribution. From 2 to 5 mol, preferablyfrom 3 to 20 mol, of at least one alkylene oxide are used per mole ofalcohol. Ethylene oxide is the preferred alkylene oxide used. Thealcohols preferably have 10 to 18 carbons.

Another class of nonionic surfactants comprises alkyl polyglucosideswith 8 to 22 carbons, preferably 10 to 18 carbons, in the alkyl chain.These compounds contain on average 1 to 20, preferably 1.1 to 5,glucoside units.

Another class of nonionic surfactants comprises N-alkylglucamides of thestructures (III) and (IV)

where A is C₆-C₂₂-alkyl, B is H or a C₁-C₄-alkyl and C ispolyhydroxyalkyl of 5 to 12 carbons and at least 3 hydroxyls. A ispreferably C₁₀-C₁₈-alkyl, B is preferably CH₃ and C is preferably a C₅or C₆ radical. Compounds of this type are obtained, for example, byacylating reductively aminated sugars with acid chlorides ofC₁₀-C₁₈-carboxylic acids. The nonionic surfactants present in thedetergent formulations are preferably C₁₀-C₁₆-alcohols ethoxylated withfrom 3 to 12 mol of ethylene oxide, particularly preferably ethoxylatedfatty alcohols.

Further suitable and preferred surfactants are the endgroup-capped fattyacid amide alkoxylates of the formula (V)

R¹—CO—NH—(CH₂)_(n)—O—(AO)_(x)—R²   (V)

where

R¹ is C₅-C₂₁-alkyl or -alkenyl,

R² is C₁-C₄-alkyl,

A is C₂-C₄-alkylene,

n is 2 or 3, and

x is from 1 to 6,

which are disclosed in WO 95/11225

Examples of such compounds are the products of the reaction ofn-butyltriglycolamine of the formula H₂N—(CH₂—CH₂O)₃—C₄H₉ with methyldodecanoate, or the products of the reaction of ethyltetraglycolamine ofthe formula H₂N—(CH₂—CH₂—O)₄—C₂H₅ with a commercial mixture of saturatedC₈-C₁₈-fatty acid methyl esters.

Builders

The pulverulent or granular detergents and, where appropriate, alsostructured liquid detergents additionally contain one or more inorganicbuilders. Suitable such substances are all conventional inorganicbuilders, such as alumosilicates, silicates, carbonates and phosphates.

Examples of suitable inorganic builders are alumosilicates havingion-exchanging properties, such as zeolites. Various types of zeoliteare suitable, especially zeolites A, X, B, P, MAP and HS, in their Naform or in forms in which Na is partly replaced by other cations such asLi, K, Ca, Mg or by ammonium. Suitable zeolites are described, forexample, in EP-A-0 038 591, EP-A-0 021 491, EP-A-0 087 035, US 4 604224, GB-A-2 013 259, EP-A-0 522 726, EP-A-0 384 070 and WO 94/24251.

Other suitable inorganic builders are, for example, amorphous orcrystalline silicates, such as amorphous disilicates, crystallinedisilicates, such as the phyllosilicate SKS-6 (manufacturer: HoechstAG). The silicates can be employed in the form of their alkali metal,alkaline earth metal or ammonium salts. Ni, Li and Mg silicates arepreferably employed.

Further appropriate inorganic builder substances are carbonates andbicarbonates, which can be employed in the form of their alkali metal,alkaline earth metal or ammonium salts. Preference is given to employingNa, Li and Mg carbonates and bicarbonates, especially sodium carbonateand/or sodium bicarbonate.

The inorganic builders can be present in the detergents in amounts offrom 0 to 60% by weight, together with organic cobuilders which are usedif desired. The inorganic builders can be incorporated, either alone orin any combination with one another, into the detergent. They are addedto pulverulent or granular detergents in amounts of from 10 to 60% byweight, preferably from 20 to 50% by weight. Inorganic builders areemployed in structured (multiphase) liquid detergents in amounts of upto 40% by weight, preferably up to 20% by weight. They are suspended inthe liquid formulation constituents.

Pulverulent, granular and liquid detergent formulations contain organiccobuilders in amounts of from 0.1 to 20% by weight, preferably inamounts of from 1 to 15% by weight, together with the inorganicbuilders. The pulverulent or granular heavy duty detergents mayadditionally include, as other customary constituents, a bleachingsystem consisting of at least one bleach, combined if desired with ableach activator and/or a bleach catalyst.

Bleaches

Suitable bleaches are perborates and percarbonates in the form of theiralkali metal salts, especially their Na salts. They are present in theformulations in amounts of from 5 to 30% by weight, preferably from 10to 25% by weight. Other suitable bleaches are inorganic and organicperacids in the form of their alkali metal or magnesium salts, or insome cases in the form of the free acids. Examples of suitable organicpercarboxylic acids or salts thereof are Mg monoterephthalate,phthalimidopercaproic acid, and diperdodecane-1,10-dioic acid. Oneexample of an inorganic peracid salt is potassium peroxomonosulfate(Oxone).

Examples of suitable bleach activators are

acylamines, such as tetraacetylethylenediamine, tetraacetylglycoluril,N,N′-diacetyl-N,N′-dimethylurea and1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine

acylated lactams, such as acetylcaprolactam, octanoylcaprolactam andbenzoylcaprolactam

substituted phenol esters of carboxylic acids, such as Naacetoxybenzenesulfonate, Na octanoyloxybenzenesulfonate and Nanonanoyloxybenzenesulfonate

acylated sugars, such as pentaacetylglucose

anthranil derivatives, such as 2-methylanthranil or 2-phenylanthranil

enol esters, such as isopropenyl acetate

oxime esters, such as O-acetyl acetone oxime

carboxylic anhydrides, such as phthalic anhydride or acetic anhydride.

Tetraacetylethylenediamine and Na nonanoyloxybenzenesulfonate arepreferably employed as bleach activators. The bleach activators areadded to heavy duty detergents in amounts of from 0.1 to 15% by weight,preferably in amounts of from 1.0 to 8.0% by weight, particularlypreferably in amounts of from 1.5 to 6.0% by weight.

Suitable bleach catalysts are quaternized imines and sulfone imines, asdescribed in U.S. Pat. No. 5,360,568, U.S. Pat. No. 5,360,569 and EP-A-0453 003, and Mn complexes, see WO 94/21777. If bleach catalysts are usedin the detergent formulations, they are present therein in quantities ofup to 1.5% by weight, preferably up to 0.5% by weight, and in the caseof the highly active manganese complexes in quantities of up to 0.1% byweight.

Enzymes

The detergents preferably contain an enzyme system. This comprisesproteases, lipases, amylases and cellulases normally employed indetergents. The enzyme system may be confined to a single enzyme or maycomprise a combination of various enzymes. The commercial enzymes areadded to the detergents, in general, in amounts of from 0.1 to 1.5% byweight, preferably from 0.2 to 1.0% by weight, of the formulated enzyme.Examples of suitable proteases are Savinase and Esperase (manufacturer:Novo Nordisk). An example of a suitable lipase is Lipolase(manufacturer: Novo Nordisk). An example of an appropriate cellulase isCelluzym (manufacturer: Novo Nordisk).

Other customary constituents

As other customary constituents, the detergents preferably contain soilrelease polymers and/or graying inhibitors (antiredeposition agents).Examples of these are polyesters of polyethylene oxides with ethyleneglycol and/or propylene glycol and aromatic dicarboxylic acids oraromatic and aliphatic dicarboxylic acids, or polyesters of polyethyleneoxides, which are endgroup-capped at one end, with dihydric and/orpolyhydric alcohols and dicarboxylic acids. Polyesters of this kind areknown; see U.S. Pat. No 3,557,039, GB-A-1 154 730, EP-A-0 185 427,EP-A-0 241 984, EP-A-0 241 985, EP-A-0 272 033 and U.S. Pat. No5,142,020.

Further suitable soil release polymers are amphiphilic graft polymers orcopolymers of vinyl and/or acrylic esters on polyalkylene oxides, seeU.S. Pat. No 4,746,456, U.S. Pat. No 4,846,995, DE-A-3 711 299, U.S.Pat. No 4,904,408, U.S. Pat. No 4,846,994 and U.S. Pat. No 4,849,126, ormodified celluloses, such asmethylcellulose, hydroxypropylcellulose orcarboxymethylcellulose.

Graying inhibitors and soil release polymers are present in thedetergent formulations in proportions of from 0 to 2.5% by weight,preferably from 0.2 to 1.5% by weight, particularly preferably from 0.3to 1.2% by weight. Soil release polymers which are preferably employedare the graft polymers of vinyl acetate on polyethylene oxide ofmolecular mass 2,500-8,000 in a weight ratio of 1.2:1 to 3.0:1, knownfrom U.S. Pat. No 4,746,456, and also commercial polyethyleneterephthalate/polyoxyethylene terephthalates of molecular mass3,000-25,000 from polyethylene oxides of molecular mass 750-5,000 withterephthalic acid and ethylene oxide, and with a molar ratio ofpolyethylene terephthalate to polyoxyethylene terephthalate of 8:1 to1:1, and the block polycondensation products known from DE-A-44 03 866,which contain blocks of ester units of polyalkylene glycols with amolecular mass of 500-7,500 and aliphatic dicarboxylic acids and/ormonohydroxymonocarboxylic acids, and blocks of ester units of aromaticdicarboxylic acids and polyhydric alcohols. These amphiphilic blockcopolymers have molecular masses of 1,500-25,000.

A typical pulverulent or granular heavy duty detergent may, for example,have the following composition:

3-50, preferably 8-30, % by weight of at least one anionic and/ornonionic surfactant,

5-50, preferably 15-42.5, % by weight of at least one inorganic builder,

5-30, preferably 10-25, % by weight of an inorganic bleach,

0.1-15, preferably 1-8, % by weight of a bleach activator,

0-1, preferably not more than 0.5, % by weight of a bleach catalyst,

0.05-5, preferably 0.2-2.5, % by weight of a color transfer inhibitorbased on water-soluble homopolymers of N-vinylpyrrolidone orN-vinylimidazole, water-soluble copolymers of N-vinylimidazole andN-vinylpyrrolidone, crosslinked copolymers of N-vinylimidazole andN-vinylpyrrolidone having a particle size of 0.1-500 μm, preferably upto 250 μm, which copolymers contain 0.01-5, preferably 0.1-2, % byweight of N,N′-divinylethyleneurea as crosslinking agent. Other colortransfer inhibitors are water-soluble and also crosslinked polymers of4-vinylpyridine N-oxide, which are obtainable by polymerizing4-vinylpyridine and then oxidizing the polymers;

0.1-20, preferably 1-15, % by weight of at least one novel mixture ofcomponents (a), (b) and (c),

0.2-1.0% by weight of protease,

0.2-1.0% by weight of lipase,

0.3-1.5% by weight of a soil release polymer,

less than 24, preferably not more than 20, preferably not more than 10,% by weight of triphosphate, and especially no triphosphate, and

according to one embodiment, not more than 20, preferably not more than10, % by weight of LAS, and especially no LAS, the total amount of theingredients being 100% by weight.

A bleaching system is often entirely or partly dispensed with incolor-sparing specialty detergents (for example in color detergents). Atypical color detergent in pulverulent or granular form may have, forexample, the following composition:

3-50, preferably 8-30, % by weight of at least one anionic and/ornonionic surfactant,

10-60, preferably 20-55, % by weight of at least one inorganic builder,

0-15, preferably 0-5, % by weight of an inorganic bleach,

0.05-5, preferably 0.2-2.5, % by weight of a color transfer inhibitor(see above),

0.1-20, preferably 1-15, % by weight of at least one novel mixture ofcomponents (a), (b) and (c),

0.2-1.0% by weight of protease,

0.2-1.0% by weight of cellulase,

0.2-1.5% by weight of a soil release polymer, for example a graftpolymer of vinyl acetate and polyethylene glycol,

less than 24, preferably not more than 10, % by weight of triphosphate,and especially no triphosphate, and

according to one embodiment, not more than 20, preferably not more 10, %by weight of LAS, and especially no LAS, the total amount of theingredients being 100% by weight.

As other customary constituents the pulverulent or granular detergentsmay contain up to 60% by weight of inorganic fillers. Sodium sulfate isnormally used for this purpose. However, the detergents of the inventionpreferably have a low filler content of up to 20% by weight,particularly preferably up to 8% by weight.

The bulk or apparent density of the novel detergents may vary in therange from 300 to 950 g/l. Modern compact detergents generally have highbulk densities, such as 550-950 g/l, and a granular structure.

The novel liquid detergents contain, for example,

5-60, preferably 10-40, % by weight of at least one anionic and/ornonionic surfactant,

0.05-5, preferably 0.2-2.5, % by weight of a color transfer inhibitor(see above),

0.1-20, preferably 1-15, % by weight of at least one novel mixturedescribed above,

0-1.0% by weight of protease,

0-1.0% by weight of cellulase,

0-1.5% by weight of a soil release polymer and/or graying inhibitor,

0-60% by weight of water, and

0-10% by weight of alcohols, glycols such as ethylene glycol, diethyleneglycol or propylene glycol, or glycerol, the total amount of theingredients being 100% by weight.

The detergents may, where appropriate, comprise further customaryadditives. Examples of other additives which may be present whereappropriate are complexing agents, phosphonates, fluorescent whiteners,dyes, perfume oils, foam suppressants and corrosion inhibitors.

Using the novel mixtures, the detergent formulations indicated below canbe prepared. Compositions A-M are compact detergents, N and O areexamples of color detergents, and formulation P is a structured liquiddetergent. The meanings of the abbreviations are as follows:

TAED: Tetraacetylethylenediamine Soil release additive 1: Polyethyleneterephthalate/- polyoxyethylene terephthalate in a molar ratio of 3:2,molecular mass of the co-condensed polyethylene glycol 4,000, molecularmass of the polyester 10,000 Soil release additive 2: Graft polymer ofvinyl acetate on polyethylene glycol of molecular mass 8,000, molecularmass of the graft polymer 24,000 EO: Ethylene oxide.

Detergent compositions A-P Constituents A B C D E F G H I J K L M N O Plin. alkylbenzenesulfonate 6 6 1 8 9 7.5 2.5 7 C₁₂-C₁₈ alkylsulfate 9 92 3 12 1.5 10 9 9 9 9 5 9 2 C₁₂ fatty alcohol × 2 EO sulfate 3 2 C₁₂-C₁₈fatty alcohol × 4 EO 3 4.5 4 4 C₁₂-C₁₈ fatty alcohol × 7 EO 10 10 13.5 4C₁₃-C₁₅ oxo alcohol × 7 EO 7 5 8 10 10 10 C₁₃-C₁₅ oxo alcohol × 11 EO4.5 3 2 7 C₁₆-C₁₈ glucamide 4 C₁₂-C₁₄ alkyl polyglucoside 4 C₈-C₁₈ fattyacid 6 methyltetraglycol amide Soap 2 2 1 0.5 2 0.5 0.6 1 2 2 2 2 1.5 2Na metasilicate × 5.5 H₂O 2 2 3.5 3 2 2 2 2 Na silicate 8 2.5 4 0.5 Mgsilicate 0.8 0.5 Zeolite A 18 24 36 35 15 30 36.5 25 20 36 24 36 36 5525 Zeolite P 18 36 Philosilicate SKS 6 (Hoechst 12 14 12 AG) Amorphoussodium discilicate 12 12 Sodium carbonate 12 12 12 11 15 10.5 10 8 12 1212 6 Sodium bicarbonate 9 6.5 Sodium citrate 5 7 4 4 TAED 4 4 3.5 3.55.5 3 4 3.8 5 4 4 4 4 Perborate 4-H₂O 20 20 24 Perborate 2-H₂O 15 14.5Percarbonate 15 15 18 20 15 15 15 15 Carboxymethyl- 1 1 1.5 2.5 0.5 2 11.3 1.5 1 1 1 1 1 1 cellulose Soil release additive 1 0.8 0.8 0.8 0.50.5 0.5 0.5 0.5 0.5 Soil release additive 2 0.5 0.5 Lipase 0.2 0.5 0.50.5 0.5 0.5 0.5 Protease 0.5 0.5 0.5 0.5 0.5 0.5 1 0.5 Cellulase 0.3 0.20.2 Sodium sulfate 3 3 3 1.5 3.5 3 3.5 2.4 3 3 2.4 1.3 2 EthanolCobuilder 1 5 5 5 5 5 5 8 5 5 5 5 5 5 5 5 15 Phosphonate 0.2 0.2 0.5Fluorescent whitener 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 Color transferinhibitor 1.5 1 Water 3.5 3.5 0.3 1 1 1 22.5 11 40.6

Rinse aid formulations

The mixtures of (a), (b) and (c) as described above are used inaccordance with one embodiment of the invention in rinse aidformulations, especially as encrustation inhibitors and/or scaleinhibitors.

The preferred embodiments of the compositions and quantities (amounts,proportions) indicated above apply to the rinse aid formulations aswell.

The dishwashing compositions can be pulverulent or else can be presentin liquid formulation. The composition of the dishwashing compositionsmay vary greatly. They include, commonly, sodium citrate, sodiumcarbonate and sodium disilicate. Rinse aid formulations are set outbelow by way of example.

Rinse aid formulations A-P Ingredients A B C D E F G H I K L M N O P Nacitrate * 2H₂O 30 20 — — 20 30 35 45 — 35 — — — — — Na carbonate — 20 34— 40 27 25 15 — 15 10 5 20 — — Na hydrogencarbonate — — — 47 — 27 7 1567 — — — 35 — — Na disilicate 31.2 15 29 10 24 — 15 5 — — — — — — —Crystalline Na silicate — — — — — — — — — 25 — — — — — (δ-Na₂Si₂O₅) Nametasilicate — — — — — — — — — — 50 31 — — — Na triphosphate — — — — — —— — — — 20 — 30 — — Complexing agents⁽¹⁾ — 5 10 — — — — — 15 — — 20 — —20 Sodium hydroxide — — — — — — — — — — — 20 — — — Aqueous KOH solution— — — — — — — — — — — — — 60 60 Na perborate monohydrate 4 4 — — 7 7 5 88 — — 15 — — — Na perborate tetrahydrate 8 8 — — — — — — — — — — — — —Na percarbonate — — 15 15 — — — — — 12 — — 15 — — TAED 4 4 2 2 2 2 — 3 33 — 4 3 — — Nonionic low-foam surfactant 1.5 1.5 2 2 2 2 4 2 2 2 2 2 2 —— Enzymes (protease + amylase) 4 4 3 3 — — 3 2 2 3 — — 3 — —Phosphonate⁽²⁾ 0.3 — — — — — — — — — — — — 1 — Na gluconate — — — 15 — —— — — — — — — — — Polymeric scale inhibitor 7 6 5 6 5 5 6 5 3 6 3 3 2 64 Na sulfate 10 12.5 — — — — — — — — 13 — — — — Na dichloroisocyanurate— — — — — — — — — — 2 — — — — Potassium waterglass (30%) — — — — — — — —— — — — — 7 5 Water — — — — — — — — — — — — — 26 11 ⁽¹⁾NTA, MGDA, EDDS,ADA ⁽²⁾HEDP, PBTC, ATMP

In the text below, the novel mixtures, detergents and cleaningcompositions are illustrated in more detail with reference to examples.Unless specified otherwise, percentages are by weight.

EXAMPLE 1

Preparation of tallow fatty amine phosphoric acid salt

535 g of tallow fatty amine are dissolved in 1500 ml of acetone, and 261g of 75% strength phosphoric acid are added with stirring. Theprecipitate is filtered off using a suction filter and dried. The yieldis 720 g. The salt has a wax-like consistency.

EXAMPLE 2

Preparation of tallow fatty amine phosphoric acid salt

13.5 g of tallow fatty amine are melted at 60° C. in a glass beaker and,while stirring with a spatula, 6.5 g of 75% strength phosphoric acid areadded. The temperature of the paste rises. Cooling gives a soft waxwhich is easy to cut up.

EXAMPLE 3

20 g of the salt prepared in Example 1 are placed in a 100 mlround-bottomed flask which is flushed with nitrogen, and are heated at200° C. for 4 hours. After cooling, the wax-like contents are comminutedand analysed. The product consists ⅓ of tallow fatty amine phosphoricacid salt and ⅔ of a condensation product of tallow fatty amine andphosphoric acid.

EXAMPLE 4

Preparation of tallow fatty amine polyphosphoric acid salt

56 g of tallow fatty amine are dissolved at 70° C. in 150 ml of toluene,and 16 g of polyphosphoric acid are added over the course of 15 minutes.The resulting precipitate is filtered off with suction and dried.

EXAMPLE 5

13.7 g of tallow fatty amine are dissolved at 60° C. in 40 g ofglycerol, and 6.5 g of 75% strength phosphoric acid are added. A viscouspaste is obtained.

EXAMPLES 6-8

Tallow fatty amine, a reaction product of a C₁₆/C₁₈-oxo alcohol with 7mol of ethylene oxide (nonionic surfactant), and water are prepared at60° C. in a glass beaker in accordance with Table 1, and 75% strengthphosphoric acid is added. Viscous pastes are obtained which on coolingsolidify to give soft wax-like substances.

TABLE 1 75% Tallow fatty Nonionic phosphoric Example amine surfactantWater acid No. [g] [g] [g] [g] 6 50 20 30 32 7 50 40 10 32 8 30 40 30 14

Preparation of the blends

EXAMPLE 9

Aqueous solutions of polycarboxylates in the sodium form are admixedwith tallow fatty amine phosphoric acid salt in accordance with Table 2,and the mixtures are very finely dispersed using a dispersion apparatus(Ultra Turrax). Depending on the polymer, the result varies from clearsolutions to cloudy suspension.

TABLE 2 Tallow fatty Tallow fatty amine amine Solids 100 g of phosphoricphosphoric content polymer acid salt acid salt of the Example solutionfrom Ex. 1 from Ex. 4 Blend mixture No. No. [g] [g] appearance [%] 9 14.0 — S 43 10 2 4.3 — L 48 11 3 4.5 — S 50 12 4 4.5 — S 46 13 1 — 4.0 S44 14 2 — 4.3 L 48 15 3 — 4.5 S 48 16 4 — 4.5 S 45

Polymer No.1: Copolymer of maleic acid and acrylic acid in a ratio of70:30 in the form of the sodium salt, 40% strength, molecular weight70,000

Polymer No.2: Copolymer of maleic acid and diisobutene in the form ofthe sodium salt, 44% strength, molecular weight 4,000

Polymer No.3: Polyacrylic acid in the form of the sodium salt, 45%strength, molecular weight 8,000

Polymer No.4: Polyaspartic acid, sodium salt, 42% strength, molecularweight 30,000

S: cloudy solution

L: clear solution

EXAMPLE 17

40 g of a maleic anhydride-isobutene copolymer with a molecular weightof 6,000 (which is in the anhydride form) are suspended in 40 ml ofwater, and 4 g of tallow fatty amine phosphoric acid salt are added. Thesuspension is neutralized with 50% strength by weight sodium hydroxidesolution until the pH of the solution is 7-8 and the polymer hasdissolved. The solids content of the solution is 44%.

EXAMPLE 18

40 g of the polymer from Example 17 are suspended in 40 ml of water, 4 gof tallow fatty amine polyphosphoric acid salt are added, and hydrolysisis carried out with sodium hydroxide solution. The solids content of theresulting solution is 43%.

EXAMPLE 19

0.1 kg of the tallow fatty amine phosphoric acid salt from Example 1 ismixed in a paddle mixer with 0.9 kg of a pulverulent copolymer of 70%acrylic acid and 30% maleic acid in the sodium salt form which has beenprepared by spray drying an aqueous solution. A powder with goodfree-flow properties is obtained.

0.05 kg of the powder mixture is mixed in a paddle mixer with 0.95 kg ofa pulverulent detergent until uniform distribution is attained.

The resulting powder detergent C then has the following composition:

Zeolite A 36% Sodium carbonate 12% Na dodecylbenzenesulfonate 6% NaC₁₂/C₁₈-alkyl sulfate 2% Soap 1% Reaction products of C₁₃/C₁₅-oxoalcohol 7% and 7 mol of ethylene oxide Na metasilicate × 5 H₂O 3.5% TAED3.5% Tylose CR 1500 1.5% Sodium sulfate 3% Na perborate monohydrate 15%Water 4.5% Mixture of 10% tallow fatty amine 5% phosphoric acid salt and90% copolymer of 70% acrylic acid and 30% maleic acid in the sodium form

Using the novel mixtures from Examples 1 to 8, the detergentformulations described in Table 3 were prepared using the powderdetergent C.

Table 3 contains the results obtained in the course of testing theencrustation-inhibiting action. The detergent formulations described inthe table were used for washing cotton test fabric. The number ofwashing cycles was 15. After this washing operation, the ash content ofthe fabric was determined by incinerating each of the test fabrics.

Washing conditions Machine: Launder-o-meter from Atlas, Chicago Numberof wash cycles: 15 Wash liquor: 250 ml of liquor Washing period: 30 minat 60° C. Detergent dosage: 4.5 g/l Water hardness: 22.4° dH [Germanhardness] (4 mmol Ca/l; Ca:Mg = 4:1) Test fabric: 20 g of cottoncheesecloth

TABLE 3 Inhibition of encrustation by various cobuilders and mixturesDetergent Content of Cobuilder formu- mixture in Compara- mixtureslation in the tive according to accordance formulation Ash Exampleexample Example with Table 2 [%] [%] 20  9 C 5 1.89 21 10 C 5 1.05 22 11C 5 2.07 23 12 C 5 3.2 24 13 C 5 1.37 25 14 C 5 0.59 26 15 C 5 0.6 27 16C 5 1.22 1 none added C 0 5.2 2 polymer C 5 3.87 solution 1 3 polymer C5 3.35 solution 2 4 polymer C 5 2.89 solution 3 5 polymer C 5 4.38solution 4

From the results in Table 3 it is evident that the formulation of ash intest fabrics is considerably reduced when the novel mixtures are used.This corresponds to a substantially improved inhibition of encrustationon the fabric.

Dishwashing compositions

The dishwashing composition E was formed by mixing, and has thefollowing composition:

sodium citrate * 2H₂O 20% sodium disilicate, amorphous 24% sodiumcarbonate 40% sodium perborate * 1H₂O  7% TAED  2% nonionic low-foamsurfactant  2% scale inhibitor  5%

Examples of the scale inhibitor are as follows:

a) mixture of 10% tallow fatty amine phosphoric acid salt and 90%copolymer of 70% acrylic acid and 30% maleic acid in the sodium form

b) mixture of 10% tallow fatty amine phosphoric acid salt and 90%copolymer of 50% maleic acid and 59% isobutene in the sodium form

c) mixture of 10% tallow fatty amine phosphoric acid salt and 90%polyacrylic acid (MW: 8000) in the sodium form

d) mixture of 10% tallow fatty polyamine phosphoric acid salt and 90%polyacrylic acid

The test for scale-inhibiting action is carried out by using 4 g of theabovedescribed rinse aid formulation per liter of drinking water of 10°dH [German hardness]. In a domestic dishwasher of type Miele G 590 SC,15 wash cycles are conducted with a load consisting of black porcelainplates, knives and glasses. After the 15 wash cycles, the load wasassessed visually. The rating 0 denotes that even after 15 cycles noscale can be seen on the load, whereas the rating 9 denotes very severescale. The ratings 1-8 are grades lying between the ratings 0 and 9. Thewashing results are indicated in the table. As can be seen from thattable, the mixtures of amines and phosphoric acid and polycarboxylateare better scale inhibitors than the polycarboxylates usedconventionally.

TABLE 4 Dishwashing compositions E Comparative Rating on Example ExampleAddition of polymer Plastic Porcelain Knife Glass 6 none 9 5 6 7 7 Napolyacrylate 9 3-4 4 4 MW: 8000 8 Copolymer Na-MA/AA 4-5 4 2-3 4 MW:70,000 9 Copolymer Na-MA/IB 4-5 2-3 2 4 MW: 4000 28 c 3-4 2 2 3-4 29 a3-4 2-3 3 3 30 b 2 1 1 1-2 31 d 2 1 1 2

We claim:
 1. A mixture suitable for inhibiting encrustation and scalingon hard surfaces, comprising: (a) from 0.1 to 99% by weight of at leastone polycarboxylate having at least 3 carboxyls, wherein thepolycarboxylate comprises at least one of the structural units selectedfrom the group consisting of acrylic acid, maleic acid, maleicanhydride, aspartic acid and, optionally, isobutene and diisobutene,which may be in the form of an alkali metal salt, (b) from 0.1 to 99% byweight of at least one amine selected from the group consisting oftallow fatty amine, hydrogenated tallow fatty amine, octylamine,2-ethylhdxylamine, nonylmine, decylamine, 2-propylheptylamine,undecylamine, dodecylamine, tridecylamine, cetylamine, stearylamine,palmitylamine, oleylamine, coconut fatty amine, mono-alpha-branchedsecondary amines, bis-alpha-branched secondary amines of the formula(I): R⁴R³HC—HN—CHR¹R²  (I), wherein R¹, R², R³, and R⁴ independently aresubstituted or unsubstituted C₁-C₂₀ alkyl, and amines of the formula(II): R⁵NR⁹—[(CR⁷R⁸)m—NH]_(n)—R⁶  (II), wherein n is an integer from 0to 20 and m is an integer from 1 to 4, R⁵ is a C₁₋₃₀ alkyl, or a C₂₋₃₀alkenyl, and each of R⁶, R⁷, R⁸, and R⁹ independently is hydrogen or isas defined for R⁵, and (c) from 0.1 to 99% by weight of at least oneacid selected from the group consisting of phosphoric acid, diphosphoricacid, triphosphoric acid, polyphosphoric acid, phosphorus acid,hypophosphorous acid, and phosphonic acid, with the proviso that themixture contains less than 24% by weight of triphosphates and the totalamount of the ingredients is 100% by weight.
 2. A method of inhibitingencrustation in detergents, comprising admixing a mixture as claimed inclaim 1 in detergents.
 3. A method of inhibiting encrustation or scalein rinse aid formulations, comprising the step of admixing a mixture asclaimed in claim 1 in rinse aid formulations.
 4. A detergent or rinseaid formulation suitable for inhibiting encrustation and scaling on hardsurfaces, comprising: at least one surfactant and a mixture comprising:(a) from 0.1 to 99% by weight at least one polycarboxylate having atleast three carboxyl groups, wherein the polycarboxylate comprises atleast one of the structural units selected from the group consisting ofacrylic acid, maleic acid, maleic anhydride, aspartic acid andoptionally, isobutene and diisobutene, which may be in the form of analkali metal salt, (b) from 0.1 to 99% by weight at least one amineselected from the group consisting of tallow fatty amine, hydrogenatedtallow fatty amine, octylamine, 2-ethylhdxylamine, nonylmine,decylamine, 2-propylheptylamine, undecylamine, dodecylamine,tridecylamine, cetylamine, stearylamine, palmitylamine, oleylamine,coconut fatty amine, mono-alpha-branched secondary amines,bis-alpha-branched secondary amines of the formula (I):R⁴R³HC—HN—CHR¹R²  (I), wherein R¹, R², R³, and R⁴ independently aresubstituted or unsubstituted C₁-C₂₀ alkyl, and amines of the formula(II):  R⁵NR⁹—[(CR⁷R⁸)m—NH]_(n)—R⁶  (II), wherein n is an integer from 0to 20 and m is an integer from 1 to 4, R⁵ is a C₁₋₃₀ alkyl, or a C₂₋₃₀alkenyl, and each of R⁶, R⁷, R⁸, and R⁹ independently is hydrogen or isas defined for R⁵, (c) at least one acid selected from the groupconsisting of phosphoric acid, diphosphoric acid, triphosphoric acid,polyphosphoric acid, phosphorous acid, hypophosphorous acid, andphosphonic acid, and optionally, other customary constituents, with theproviso that the detergent or the rinse aid contains less than 24% byweight of triphosphate.
 5. A detergent or rinse aid formulationcomprising at least one surfactant and a mixture as claimed in claim 1and, optionally, other customary constituents.
 6. A detergent or rinseaid formulation as claimed in claim 4, comprising: 0.01-40% by weight of(a), 0.01-20% by weight of (b), and 0.01-20% by weight of (c), whereinthe total amount of the ingredients being 100% by weight.
 7. A method ofinhibiting encrustation in textiles, comprising the step of cleaningtextiles with a detergent formulation as claimed in claim
 4. 8. A methodof inhibiting encrustation and scaling on hard surfaces, comprising thestep of cleaning hard surfaces with a rinse aid formulation as claimedin claim 4.